Process for preparing acylaminomethyl quaternary ammonium compounds



Patented July 28,1942, i I 2,291,519

' UNITED STATES lPA TENT OFFICE Q i rao'cn'ss FOR rnsr G AcizmmNo- -METHYL QUATERN YAMMONIUM CO m Walter Valentine Wirth, Woodstown, N. 1., and Robert Freeman Deese, Ji' Wilminzton, Dei.,

assixnors to E. L du Pont de Nen'iours &'Com- I pany, Wilmington, Del, a corporation or Delaware ' No Drawing. Application June 13, 1941,

Serial No. 397,902

a, 4 Claims. (01. zto-zssie a This inventionjgti to an improved process less point to the-desirability of further improvetor firms quaternary ammonium mmnounds ment. 4 p possessing a long-chain acyl amido radical in Thus when ketonesare employed as the liquid their structure. More particularly, this inventlon llilutefivfifi i 35 31.11 91 the desilfifik p relates to the productionof compounds of the 5 quaternary 1 9 11 is not quite so hi h s general formula when hydrocarbon solventsar'e employed. Furv thermore, the product is discolored by comparison R-CNHCH1N(C5H5) x with the product obtained when a hydrocarbon wherein R is an'alkyl radical having from 8 to 20 solvent is employed. Apparently, the hydrocarcarbon atoms in its structure X is the anion-of a 10 hon when have the Pqwer to 9 in salmonwater-soluble acid,whlle N(CtHt) represents the f f filter qut) cert-am byproduct pyridine-ring. gompmmds of the above type are impurities winch solvents of the ketone type do useiulpas water-repellency'agents, that is, renot completely dissolve" agents for rendering textile fibers wa r'r pell n Qnthe other hand the u hYdIPCarbOn' (See British Patent'No. 477,991 and U. s. Patent 15 Prmuc"! mghestmeld-and No; 2,146,392) urity has the disadvantaged slow filtration. It is an object or this invention to provide an H be that an step e t impmved process for preparing compounds of ture, the solid stearamido-methyl-pyridmium Y the above ty in good yield and in a high state ll-bride pmducedis 17. P P- h of purity. other important objects): tmimvem go solvent (and by-lgroduct impurities dissolved on wmappear as the dscnpuon pmceeds therein) by filtrati n. For somereason, however, In our earlier U. S. Patent No. 2,2l2,654, issued the hydrocarbon type solvent chugging-1%}! August 27, 1940 we'have described animproved to the.rysta1-s 9 the e t l compound process ior manufacturing compounds of the "'mtratpn is that take days w type said process m Essentials and evenweeks to produce a product of the same sisted of reacting a higher acyl amide, relative dryne ss" (l. e., freedom from solvent), I stance stearamide, with bammrmamehyde m as may be produced in a few hours where acetone inert organic liquid, in the optional presence .of ethyl'methyl fi the solvent pyridine, to produce the corresponding methylol- It f found that} the "sughtfdeficlency m amide, for instance stearamldo-methanihl. Then, yield in the case of W solvent can be without isolating the intermediate riiethylolm m m'the second step amidedurther quantities of pyridine were added larger excess ofpyridme h tr t this v it necessary and dry hydrogen chlorideywas is objectionable notonly from the viewpo nt of into the mixture to pyridine hydmcmonde economy of materials but also because the excess within the mass. The masswould their beheated 5 pyfldme. hydrochloride genera-11y staysim the to a temperature oiabout'50 to 80 C. to efiect a final product" reducing pementage 'v reaction as indicated by the following efiuation: mermm' Ermine hydmcmmdt P i v tender the fabric eventually treated with the RCONH;-CHa6H+N(Csl-I5) -HC1- product, audit is therefore liviouslyundeslrable Q i jf c +mo 40 to iicrease the proportion thereof .in the final 4 v v pro uct. A5 inert gamc liquids tor h r It is clear from all the above that the choice 7 reaction z ggg asg gfg g sfizg and agaptation or solvent for the process inquesp 611x394v [1015- v on not so sim 1e as might a ear at first er petroleum factions kewheszastypifled by thought, and that ommercial mai i zifacture imacetone, and m hYbet fly and miscelposes on theprocess problems which would not ia ggo i s ng ggggong glv m gg g i g occur 0;; would not be material .in pure scientific researc 1 round to give very esir b e-i ove ents 1n Nowaccording to ou'rpresent i vent on the yield and qua ity o t e p o and ave i en- 5 ,above economical problem or choice or, solvent eral improved theeconomy oi theprocess. Neverhas been solved successiullyby the employment theless, when manufacturing is done on a come of a. combination of solventspreierablyin a par mercial scale, it is found that some oi these solticular sequence.- More particularly. we have vents possess special characteristic disadvantages I foundit' advantageous to carry out the first step which though not fatal to the process neverthe- I! of the process. that: is.metbylol"iormation, .in a

hydrocarbon solvent, and then adding a low boilreaction mass formed 'a stiff paste on cooling ing ketone solvent to the second stage of the to about 30 C. 125 parts of diethyl ketone were process, that is the quaternization step. The added and the whole was agitated until a smooth requisite tertiary base, such as pyridine, may be slurry resulted. Dry hydrogen chloride was added either in the first step, or in the second 5 passed into the mass until it was acid. parts step, or partially in each step. The hydrogen more of pyridine were added. The reaction mass chloride is fed-in during the second step, and in was then heated to 70 0., held at 70 to 75 C. all other details the process may follow the profor 2 hours then cooled to 13 C. and filtered. cedures set forth in our prior patent above re- The filtration was complete in hour on a small ferred to. 10 Buchner suction funnel. After drying, the prod- Some improvement may also be obtained by not was recovered in high yield, in a high state using initially a mixed solvent consisting of a of purity and of relatively small pyridine hydroa liquid hydrocarbon and a liquid ketone. But chloride content. the results are not so good as with the succes- Example 3 sive arrangement above indicated. Likewise, 15 improved results may also be obtained by using 76 parts of stea amid 526 p ts of 9 a hydrocarbon solvent exclusively in both stages (a mixture of saturated aliphatic hydrocarbonsof the process only adding a liquid ketone just at least 80% boiling between 100 and 130 0.), prior to filtering. But this process requires the'35:1 parts of paraformaldehyde nd Part8 use of a larger quantity of the hydrocarbon solof pyridine were heated at 75 to 80 C. for 10 t t i tai th mass i tu bl t t hours and then cooled. Crystallization started throughout the process. Hence this alternative at about la d a n sty mass was fomledsrn is not so economical as the preferred process cooling to about C. 132 parts of acetone -\aboyeindicatedd were then. added, and a smooth slurry resulted.

' M The theory of this surprising effect i not en- 25 Dry y n chl ride was passed into the mass tirely clear to us. It is possible that the water until it s c d to Congo Red test pap t formed in the quaternization step has some in- 20 t0 Parts Of Py d e Were then fluence on the rate of filter-ability of the hydroadded d e h e was held at 60 to 65 0.

carbon solvent, and that the ketone by absorbfor four hours- The ge aS.cooled to 12 ing this water diminishes its inhibiting effect on 30 O r a Period of about 18 hours andfiltered.

the filtration. It will be noted that the low boil- The filtration w s omple e in about an hour,

i g li ui k t wh ch would naturally be The wet cake obtained was dried and gave a w available for our purpose for instance acetone, crude stearamido methyrpyridinium chloride oi dlethyl ketone or methyl-propylsketone, are at lly higlfiurity and of exceptionally low least partially miscible with water. However, fi lg' hlo ide content.

the theory ofthe observeLphenemeW Example ,essentiar o e successful practice of our 'invenl tion, and we therefore do not desire to limit this 114 parts of stearamldeeiw'parts of pyndme' invention to any particular theory. It is sur- 18 partsfif pal'aforliflaldehyde and 150 Parts of prising in any event, that the use of two solvents Pe i were agltated, heated t0 d as indicated overcomes the disadvantage o at 75 110 for 2 hours- After cooling served with each solvent individually; t is not temperature the Smooth slurry w s dioftenjin chemistry that two reagents can be luted 150 Parts of methyl'n-prwyl-ketone made to complement each. other and compensate and acidified with y h o en chloride. The for eagh other so perfe tl excess acid was neutralized with 3 parts of'pyri- Without limiting thisinvehtion, the following and Parts moreof Pyridine was addedexampie are given to illustrate our preferred The image was heated to 700 and held at 70 mode f Operation Parts mentioned are by to 75 C. for 2 hours, after which it was cooled weight. to 14 C. and filtered. The filtration was very Example 1 rapid. Drying the press cake gave a product of high quality and good yield. 114 parts of stearamlde, 45 parts of pyridine. 113 parts oj paraformaldehyde and 150 parts of Ewample 5 igluenewere mixed'and held 12 hours at 75 to 114 parts of stearamide, 45 parts of pyridine,

80 C. The mass was cooled slowly to 25 C. 18 parts of paraformaldehyde and-150 parts of and a fairly tifi paste resulted. 150 parts of Ii-29 (boiling range 80 to 130 C.) were agiacetone was added and the whole stirred until tated and heated for 12 hours at 75 to' 80C. a smooth slurry resulted. Dry hydr'ogenchlo- After cooling to 25 C., 150 parts of methylisoride was passed into the mass at about 30 C. butyl-ketone was added. A thin slurry of the until the charge was acid. 10 part more of methylol stearamide was formed, into which dry pyridine was-added and the charge held at 6 hydrogen chloride was passed at 20 to 35 C. to C. for four hours after which it was cooled until the mass acid'to Congo Red. The exto about 15 C. and filtered. Very rapid filtracrass/acid was neutralized with 3 parts of pyrition resulted. The wet cake was dried and ar -dine and 7parts excess pyridine was added. Afthigh yield cl crude stearamido methyl pyridinium 65 er heating at to C. for 2 hours, the chloride was obtained in a state of high purity charge was cooled to 13 C. and filtered. The and containing a relatively small proportion of filtration was very rapid and resulted in a product of exceptionally high qualities and yield. Example 2 Example 6 114 parts of tearamide, 45 parts of pyridine, 70 114 parts of stearamide, 5 parts of pyridine, 18 16. parts of paraformaldehyde and 150 parts'of parts of paraformaldehyde and 150 parts of Dependip (a mixture of'saturated 'hydrocar- Dependip were mixed and held for 17 hours bone-90% boiling between 120 and 139 C.) were at 75 to C. The methylol stearamide parmlxed and held six hours at to C. The 75 i y P pitated out. Th s ot was then v r a,2o 1',u a-

added to 150 of methyl ethyl-ketone con-- above; examples may also be formed by dissolving dry hydrogen chloride in the selected ketone.

e. g.,' acetone, 'at to 5 C. and'the'n adding this .ketone solution to the slurry of methylol stear- .amide in the mixture of pyridine and hydrocarbons.

As already mentioned, some improvement in both yield and purity of product may be ob- I tained also by using initially a mixture of hydrocarbon and ketone.

The following additional thisprocedure.

example illustrates Example 7 --ll4 parts of stearamide, 18 parts of paraformaldehyde, 45 parts of pyridine, 150' parts of methyl-ethyl-ket'one and 150 parts of Dependip" were heated together and held for 10 hours at 75 to 80 C. The mass was cooled to C. tov

form a smooth slurry. After acidifying with dry hydrogen chloride, 10 parts of pyridine was added to'in'sure a neutral solution and' the whole was heated for 4 hours at about 63 C. The mass was then cooled to 14 0. and flltered.- The flltration was .quite rapid, and gave a product of high qualtity and'good color compared to-the product obtained by using a ketone alone as solvent. 1

While the a ve examples have employed stearamide as-initia1 material in each case, it will be clear that the same process may be ap-' plied also to other higher fatty acid amides, such medium consisting at least in part of a hydrocarbon solvent, then reacting the resulting mass with a pyridinium salt oh... the formula N(C5H5) 'HX in-the presence of-free pyridine, and Y in the further presence of a liquid dialkyl ketone which is adapted to absorb the water of formation in the reaction mass.

2. A rocess of producing an"acylamido- -methyl-pyridinium halide-of the formula wherein It stands for an alkyl radical having at least 8.carbon atoms, N(C5Hs) designates a pyri dine ring, while Hal" stands for halogen, which comprises reacting the corresponding acylamide 1 of formula R,.CONI-Ia with paraformaldehyde in a liquid medium consisting at least partly of a liquid hydrocarbon to-produce in s'itu a methylol compound of the formula g v .HONHi-CHzOH v p I then adding to'the reaction mass a liquid ketone which is at least--partially watenmiscible, and

' stages.

em dry hydrogen halide into the reaction 'mixture after having added pyridine to the reaction mass at least during one of theabove two a A proc of. producing an acylamidome hyl-pyridinium chloride, whereof the acyl group contains at least 8 carbon atoms, which comprises reacting the corresponding acyla'midewith paraformaldehydedn a liquid medium consisting essentially of a liquid hydrocarbon and pyridine, then adding to the reaction mass a liquid dialkyl ketone and such further quantities of pyridine as may be necessary to bring up the total quantity of pyridine in the mass to at least one mole per mole of 'acylamide initially employed, feeding in dry hydrogen chloride to form as. lauramide or palmitamide, to produce the corresponding acyl-amido-methylene-pyridinium chlorides in improved yield and quality. Likewise in lieu of the ketones specifically named,

any other dialkyl ketone may be employed'provided it is liquid within the range of temperatures employed (say 20 to '100" C.) and is at a those skilled in the art without departing from the spirit of this invention. We claim: 1. The process of producing a. quaternary, am-

pyridine-hydrogen-halide in the reaction mass,

' adding an excess, of pyridine, warming the .re- "action mass to effect reaction between the intermediate acylamido-methylol compound and the pyridine-hydrogen-halide, and isolating the solid reaction product by filtration,

4. A process of producing stearamido-methylpyridinium chloride, which comprises reacting stearamide with paraformaldehyde in a medium consisting essentially f a liquid hydrocarbon containing sufficient pyridine to provide at least one molezof pyridine permole of initial stearamide; then adding to the reaction mass a liquid dialkyl-ketorieadapted to absorb the water of monium compound of the general formula v R-coNH-cgia-mcmo-x wherein R .is an alkyl radical having .at least 8 carbon atoms, X. is the anion of a water-soluble acid, while N(C5Hs) designates the pyr dine ring, which comprisesiirst reacting the -correspending acyl amide of the formula m-comn with paraformaldehyde in an organic liquid formation in the subsequent quatemization step;

feeding in hydrogen chloride until-the mass ascrimes-substantially an acid reaction; neutralizing the excess acidity with further quantities of pyridine, warming the reaction mass to a temperature of about 60 to '7? C., and filtering oil thesolid reaction product thus obtained.-

.WAL

TEE VALENTINE WIR'I'H. RQBER-T FREEMANDEESE, J R. 

